US8323532B2 - Positive electrode material formed by a lamellar-type oxide for a lithium battery - Google Patents
Positive electrode material formed by a lamellar-type oxide for a lithium battery Download PDFInfo
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- US8323532B2 US8323532B2 US12/996,510 US99651009A US8323532B2 US 8323532 B2 US8323532 B2 US 8323532B2 US 99651009 A US99651009 A US 99651009A US 8323532 B2 US8323532 B2 US 8323532B2
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 57
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000007774 positive electrode material Substances 0.000 title description 5
- 239000011149 active material Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 10
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 3
- 229910052729 chemical element Inorganic materials 0.000 claims description 26
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 24
- 229910052748 manganese Inorganic materials 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 229910052720 vanadium Inorganic materials 0.000 claims description 8
- 229910011104 LiM1 Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 5
- 230000000171 quenching effect Effects 0.000 claims description 5
- 229910002983 Li2MnO3 Inorganic materials 0.000 claims description 4
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 230000001351 cycling effect Effects 0.000 abstract description 15
- 239000011572 manganese Substances 0.000 description 34
- 150000001875 compounds Chemical class 0.000 description 28
- 239000011777 magnesium Substances 0.000 description 28
- 229910001416 lithium ion Inorganic materials 0.000 description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 239000000463 material Substances 0.000 description 10
- 229910013191 LiMO2 Inorganic materials 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- -1 poly(acrylonitrile) Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 4
- 229910016087 LiMn0.5Ni0.5O2 Inorganic materials 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- 229910005143 FSO2 Inorganic materials 0.000 description 2
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002641 lithium Chemical class 0.000 description 2
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910011279 LiCoPO4 Inorganic materials 0.000 description 1
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 1
- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910013084 LiNiPO4 Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 229910015718 LixMnyM1-YO2 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910000652 nickel hydride Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/125—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3
- C01G45/1257—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3 containing lithium, e.g. Li2MnO3, Li2[MxMn1-xO3
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/20—Two-dimensional structures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the invention relates to a lamellar-type oxide, in particular used as active material of a positive electrode for a lithium battery and to a method for synthesizing such an oxide.
- Lithium batteries are progressively replacing nickel-cadmium (Ni—Cd) or metallic nickel-hydride (Ni-MH) batteries as autonomous power source, in particular in portable equipment. This tendency can be explained by the continuous improvement of the performances of lithium batteries giving them substantially higher mass and volume energy densities than those of Ni—Cd and Ni-MH batteries.
- the first Li-ion type lithium batteries had a mass energy density of about 85 Wh/kg, a mass energy density of about 200 Wh/kg can be obtained at present.
- Ni—MH batteries and Ni—Cd batteries respectively have a mass energy density of 100 Wh/kg and 50 Wh/kg.
- lithium batteries have to be further improved. Improving the performances of Li-Ion batteries and in particular increasing their capacity are closely related to the search for new active electrode materials.
- the active materials generally used for negative electrodes in commercial lithium batteries are carbon (graphite, coke, . . . ), a spinel oxide of Li 4 Ti 5 O 12 type or a metal forming an alloy with lithium such as Sn or Si.
- the active materials used for positive electrodes in commercial lithium batteries are compounds of lamellar-type structure, such as LiCoO 2 and LiNiO 2 oxides, or compounds of spine structure such as LiMn 2 O 4 and derivatives thereof.
- these compounds have to be further improved and the electrode/electrolyte interface has to be stabilized at high voltage as the lifetime is about a few tens of cycles and is therefore low.
- These compounds furthermore have low theoretical specific capacities generally comprised between 145 and 170 mAh/g.
- Another possible path for improvement consists in finding active materials for the positive electrodes of lithium batteries having higher specific capacities than the active materials used at present.
- Lamellar-type oxides of LiMO 2 type, where M represents a transition element such as cobalt, do however enable theoretical capacities that are among the highest to be obtained.
- the theoretical capacities are in fact comprised between about 270 to 300 mAh/g, according to the molar mass of the transition element. In practice however, the capacity obtained is generally about 150 mAh/g, due to the obligation of preserving the structural coherence of such oxides.
- LiNi 0.8 Co 0.15 Al 0.05 O 2 and LiNi 1/3 Co 1/3 Mn 1/3 O 2 compounds also of lamellar-type structure, enable similar or substantially higher electrochemical performances to be obtained than oxides of LiMO 2 type for lower or equal cost and an improved chemical stability in particular in charged state.
- oxides of xLi 2 M′O 3 .(1 ⁇ x)LiMO 2 type where:
- Such oxides have the particularity of presenting multiple electrochemical phenomena associated with the changes of oxidation degrees of the different transition elements. This enables high specific capacities to be obtained in certain cases, paving the way for development of particularly attractive active materials. However, it is not sure that the specific capacity can be maintained with such materials when cycling takes place. A decrease of the specific capacity can in fact be observed in the course of the charging/discharging cycles. A great deal of progress therefore still remains to be made in order to propose active materials for positive electrodes enabling a high and stabilized specific capacity to be obtained, therefore providing Lithium-Ion batteries with improved performances.
- the object of the invention is to propose active materials for the positive electrode remedying the shortcomings of materials according to the prior art and in particular, in the field of lithium batteries, enabling a stabilized in cycling and high specific capacity to be obtained, advantageously at all the cycling temperatures usually used and in the usual range of potentials.
- this object is achieved by a new family of lamellar-type oxides of following general formula: x Li 2 MnO 3 .(1 ⁇ x )LiM 1 a M 2 b M 3 c O 2
- the lamellar-type oxide is represented by the following formula: 0.75Li 2 MnO 3 .0.25LiNi 0.9 Mn 0.05 Mg 0.05 O 2 .
- FIG. 1 represents the variation of the specific capacity on discharge versus the number of cycles, in intentiostatic mode (C/10 conditions, 55° C.), of Lithium batteries comprising lithium as active material for the negative electrode and respectively 0.75Li 2 MnO 3 .0.25LiNiO 2 , 0.75Li 2 MnO 3 .0.25LiNi 0.6 Mg 0.2 Mn 0.2 O 2 and 0.7Li 2 MnO 3 .0.3LiMn 1/3 Ni 1/3 Co 1/3 O 2 as active material for the positive electrode.
- FIG. 2 represents an X-ray diffraction diagram ( ⁇ cuK ⁇ ) of the compound of formula 0.75Li 2 MnO 3 .0.25LiNi 0.9 Mn 0.05 Mg 0.05 O 2 prepared according to a first particular embodiment.
- FIG. 3 corresponds to a scanning electron microscopy image of the compound of formula 0.75Li 2 MnO 3 .0.25LiNi 0.9 Mn 0.05 Mg 0.05 O 2 prepared according to a first particular embodiment.
- FIG. 4 represents the variation of the specific capacity on discharge versus the number of cycles of a lithium battery comprising the compound 0.75Li 2 MnO 3 .0.25LiNi 0.9 Mn 0.05 Mg 0.05 O 2 as active material for the positive electrode, during testing performed in intentiostatic mode under C/10 conditions with a temperature of 55° C., between 3 and 4.8 V vs. Li + /Li.
- FIG. 5 represents the charging/discharging curve plot (potential versus specific capacity) at the hundredth cycle of a lithium battery comprising the compound 0.75Li 2 MnO 3 .0.25LiNi 0.9 Mn 0.05 Mg 0.05 O 2 as active positive electrode material, when testing is performed in intentiostatic mode between 2.5 and 4.8 V vs. Li + /Li, under C/10 conditions at a temperature of 55° C.
- FIGS. 6 and 7 represent the curve plot of the first discharge (potential versus specific capacity) of a lithium battery comprising a compound 0.75Li 2 MnO 3 .0.25LiNi 0.9 Mn 0.05 Mg 0.05 O 2 obtained according to an alternative embodiment and used as active positive electrode material, when testing is performed in intentiostatic mode between 2.5 and 4.8 V vs. Li + /Li, under C/10 conditions respectively at a temperature of 55° C. and 20° C.
- FIG. 8 represents the variation of the specific capacity on discharge versus the number of cycles (C/10 conditions) of lithium batteries the first discharge of which is plotted in FIGS. 6 and 7 .
- Lamellar-type oxides of the following general formula: x Li 2 MnO 3 .(1 ⁇ x )LiM 1 a M 2 b M 3 c O 2 (1) where:
- oxides of the general formula (1) comprise at least one electrochemically inactive chemical element (M 3 ), also called chemical element devoid of electrochemical activity.
- electrochemically inactive chemical element is a chemical element that does not oxidize or that is not reduced during charging or discharging of a lithium battery, in the usual range of potentials.
- M 3 is more particularly at least a chemical element chosen from the group formed by Mg, Zn, Al, Na, Ca, Li, K, Sc, B, C, Si, P and S. M 3 can thus also be formed by several of the chemical elements of the above-mentioned group. M 3 thereby enables the specific capacity on cycling to be indirectly stabilized.
- M 3 is further associated:
- M 1 is nickel
- M 2 is manganese
- M 3 is magnesium
- b is moreover preferably equal to c.
- the positive electrode of a lithium battery can thus comprise a majority quantity of an oxide of the general formula (1) as active material.
- the positive electrode advantageously comprises minority quantities of an organic binder such as a polyether, a polyester, a polymer with a base of methyl methacrylate, acrylonitrile, or vinylidene fluoride and an electron-conducting additive such carbon.
- the lithium battery also comprises a negative electrode the active material of which can be of any known type.
- the active material of the negative electrode can be lithium in metal form or it can be a material able to insert and de-insert Li + ions, such as carbon in general in graphite form, an oxide such as Li 4 Ti 5 O 12 or a compound forming an alloy with lithium such as silicon or tin.
- the electrolyte of the lithium battery in general comprises a lithium salt for example chosen from LiClO 4 , LiAsF 6 , LiPF 6 , LiBF 4 , LiR F SO 3 , LiCH 3 SO 3 , LiN(R F SO 2 ) 2 , LiC(R F SO 2 ) 3 , lithium bis(trifluoromethanesulphonyl)imide (also noted LiT F SI), lithium bis(oxalato)borate (also noted LiBOB), lithium bis(perfluoroethylsulfonyl)imide (also noted LiBETI), or lithium fluoroalkylphosphate (LiFAP).
- a lithium salt for example chosen from LiClO 4 , LiAsF 6 , LiPF 6 , LiBF 4 , LiR F SO 3 , LiCH 3 SO 3 , LiN(R F SO 2 ) 2 , LiC(R F SO 2 ) 3 , lithium bis(trifluoromethanesulphonyl
- R F is a radical chosen from a fluorine atom and a perfluoroalkyl group containing between one and eight carbon atoms.
- the lithium salt is further preferably dissolved in an aprotic polar solvent.
- the salt is for example supported by a separating element arranged between the two electrodes of the battery, the separating element then being imbibed with electrolyte.
- the lithium salt is not dissolved in an organic solvent, but in a solid polymer composite such as polyethylene oxide (PEO), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride (PVdF), polyvinyl chloride (PVC) or a derivative thereof.
- a solid polymer composite such as polyethylene oxide (PEO), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride (PVdF), polyvinyl chloride (PVC) or a derivative thereof.
- the voltage cycling boundary limits of the battery have to be from about 2 to 3V vs. Li + /Li for the lower limit and from about 4.6 to 4.8 V vs. Li + /Li for the upper limit.
- the mean operating voltage is generally about 3.4 to 3.8 V vs. Li + /Li on discharge.
- Example n o 1 the 0.75Li 2 MnO 3 .0.25LiNi 0.6 Mn 0.2 Mg 0.2 O 2 compound was synthesized and then tested in a lithium battery of “buttoncell” format.
- the 0.75Li 2 MnO 3 .0.25LiNi 0.6 Mn 0.2 Mg 0.2 O 2 compound is in particular obtained by intimately mixing 2 g of a previously synthesized precursor A and 1.502 g of lithium hydroxide LiON.H 2 O, by heating the mixture at 900° C. for 24 hours and then cooling it very quickly to ambient temperature (quenching).
- the precursor A was previously synthesized from:
- Characterization of the product obtained after the quenching operation confirms synthesis of the 0.75Li 2 MnO 3 .0.25LiNi .,6 Mn .,2 Mg 0.2 O 2 compound and its lamellar-type structure.
- a “buttoncell” format lithium battery is then achieved with:
- FIG. 1 The variation of the specific capacity versus the number of cycles corresponding to this lithium battery is represented by plot A in FIG. 1 .
- FIG. 1 also comprises plots B and C corresponding to the variation of the specific capacity versus the number of cycles for two similar batteries but respectively implementing 0.7Li 2 MnO 3 .0.3LiMn 1/3 Ni 1/3 Co 1/3 O 2 and 0.75Li 2 MnO 3 .0.25LiNiO 2 as active positive electrode material.
- Plot A enables it to be observed that the specific capacity obtained with the 0.75Li 2 MnO 3 .0.25LiNi 0.6 Mn 0.2 Mg 0.2 O 2 oxide is relatively constant whatever the number of cycles.
- Example n o 2 the 0.75Li 2 MnO 3 .0.25LiNi 0.9 Mn 0.05 Mg 0.05 O 2 compound was synthesized and then tested in a “buttoncell” format lithium battery similar to the one produced in example n o 1.
- the 0.75Li 2 MnO 3 .0.25LiNi 0.9 Mn 0.05 Mg 0.05 O 2 compound is in particular synthesized by intimately mixing 1.50 g of a previously synthesized precursor A′ and 1.11 g of lithium hydroxide LiOH.H 2 O, and by then heating the mixture at 1000° C. for 24 hours before cooling it very quickly to ambient temperature (quenching).
- precursor A′ was previously synthesized from:
- Precursor A′ is represented by the general formula Mn 0.7625 Ni 0.225 Mg 0.0125 (OH) 2 .
- the 0.75Li 2 MnO 3 .0.25LiNi 0.9 Mn 0.05 Mg 0.055 O 2 compound thus synthesized was characterized by X-ray diffraction ( FIG. 2 ) and by scanning electron microscopy observation ( FIG. 3 ).
- FIG. 2 enables the composition of the synthesized compound to be confirmed and
- FIG. 3 confirms the lamellar-type structure of the compound.
- Such a compound was further used as active material of a positive electrode in a “buttoncell” format lithium battery similar to the battery produced in example n o 1. Only the active material of the positive electrode was replaced in the lithium battery according to example n o 1.
- FIGS. 4 and 5 illustrate the electrochemical characteristics corresponding to this lithium battery. It can thus be observed in FIG. 4 that the specific capacity of the lithium battery is stable on cycling.
- the value of the specific capacity (plot D) is in fact substantially constant whatever the number of cycles applied.
- the mean loss of capacity per cycle is in fact estimated, over the first 80 cycles, at only 0.01%. For comparison purposes, this loss is generally about 0.04% for a commercial Lithium battery.
- FIG. 4 comprises an insert representing the first discharge (plot E) of the battery, performed in intentiostatic mode, under C/10 conditions at a temperature of 55° C., for potentials varying between 3 and 4.8V vs Li + /Li.
- Plot E thus corresponds to the variation of the potential with respect to the potential of the Li + /Li pair, versus the specific capacity.
- the specific capacity of the battery is 200 mAh/g at the first discharge.
- Plot F of FIG. 5 indicates that it is moreover possible to obtain, in the case of the 0.75Li 2 MnO 3 .0.25LiNi 0.9 Mn 0.05 Mg 0.05 O 2 compound and after 100 charging/discharging cycles:
- the mass energy is very high in comparison with that obtained with active materials used in currently marketed batteries (generally about 600 Wh/kg), all the more so as it is obtained after a large number of cycles.
- 0.75Li 2 MnO 3 .0.25LiNi 0.6 Mn 0.2 Mg 0.2 O 2 and 0.75Li 2 MnO 3 .0.25LiNi 0.9 Mn 0.05 Mg 0.05 O 2 oxides and more generally the oxide family of xLi 2 MnO 3 .(1 ⁇ x)LiM 1 a M 2 b M 3 c O 2 , type enable high capacities to be attained, while at the same time maintaining a good stability over a large number of charging/discharging cycles. In certain cases, it is possible to obtain specific capacity values or more than 300 mAh/g, which represents an increase of 100% compared with the active materials for the positive electrode used in lithium batteries, such as the LiCoO 2 oxide.
- the oxides according to the invention are advantageously prepared by thermally treating a powder obtained by mixing a precursor forming a source of elements M 1 , M 2 and M 3 in predetermined proportions with lithium hydroxide LiOH.H 2 O, at a temperature at least equal to 800° C. and more often of about 900° C. to 1000° C.
- the precursor is in particular represented by the general formula Mn x M 1 a(1-x) M 2 b(1-x) M 3 c(1-x) (OH) 2 .
- the oxide can be subjected to post-treatment in a slightly acid aqueous solution to improve its electrochemical properties and therefore the specific capacity of the lithium battery.
- Example n o 3 10 g of the 0.75Li 2 MnO 3 .0.25LiNi 0.9 Mn 0.05 Mg 0.05 O 2 compound obtained according to example n o 2 are mixed with 250 mL of an aqueous solution having a pH equal to 5.5.
- the aqueous solution is for example water in which an acid such as H 2 SO 4 or HNO 3 is added to adjust the pH.
- the mixture is then stirred for 30 minutes, and is then placed in an ultrasonic tank for 10 minutes.
- the mixture finally placed under magnetic stirring for 24 hours.
- a centrifugation operation consisting in three washings with water enables a powder to be recovered, which powder is then dried at 50° C. for 24 hours. Finally the powder is subjected to heat treatment at a temperature of 350° C., for 3 hours in air.
- the compound treated in this way is then tested as active material for the positive electrode in a “buttoncell” format battery respectively with cycling temperatures at 20° C. and at 55° C.
- the battery is similar to the batteries produced according to examples n o 1 and 2. It thus comprises the same constituents as the batteries produced according to examples n o 1 and 2, with the exception of the active material of the positive electrode.
- the specific capacity is equal to 317 mAh/g for a cycling temperature of 55° C. (plot G) and it is 252 mAh/g for a cycling temperature of 20° C. (plot H).
- the specific capacity obtained for a cycling temperature of 20° C. with active materials for the positive electrode according to the prior art is lower. For example it is about 150 mAh/g, at 20° C., for compounds of xLi 2 MnO 3 .(1 ⁇ x)LiMO 2 type.
- the mean potential on discharge is 3.656 V vs. Li + /Li at 20° C. (i.e.
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FR0803139A FR2932175B1 (fr) | 2008-06-05 | 2008-06-05 | Materiau d'electrode positive forme d'un oxyde de type lamellaire pour accumulateur au lithium. |
PCT/FR2009/000625 WO2009147315A1 (fr) | 2008-06-05 | 2009-05-28 | Matériau d'électrode positive formé d'un oxyde de type lamellaire pour accumulateur au lithium. |
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JP5586532B2 (ja) | 2011-06-23 | 2014-09-10 | 株式会社東芝 | 非水電解質電池及び電池パック |
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US11362331B2 (en) | 2016-03-14 | 2022-06-14 | Apple Inc. | Cathode active materials for lithium-ion batteries |
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JP2011522383A (ja) | 2011-07-28 |
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FR2932175B1 (fr) | 2011-06-03 |
ATE533732T1 (de) | 2011-12-15 |
EP2318315B1 (de) | 2011-11-16 |
PL2318315T3 (pl) | 2012-04-30 |
KR20110031420A (ko) | 2011-03-28 |
FR2932175A1 (fr) | 2009-12-11 |
WO2009147315A1 (fr) | 2009-12-10 |
CN102056844B (zh) | 2013-09-04 |
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